Bacteria associated with Zn-hyperaccumulators Arabidopsis halleri and Arabidopsis arenosa from Zn-Pb-Cd waste heaps in Poland as promising tools for bioremediation.

To identify metal adapted bacteria equipped with traits positively influencing the growth of two hyperaccumulator plant species Arabidopsis arenosa and Arabidopsis halleri, we isolated bacteria inhabiting rhizosphere and vegetative tissues (roots, basal and stem leaves) of plants growing on two old Zn-Pb-Cd waste heaps in Boleslaw and Bukowno (S. Poland), and characterized their potential plant growth promoting (PGP) traits as well as determined metal concentrations in rhizosphere and plant tissues. To determine taxonomic position of 144 bacterial isolates, 16S rDNA Sanger sequencing was used. A metabolic characterization of isolated strains was performed in vitro using PGP tests. A. arenosa and A. halleri accumulate high amounts of Zn in their tissues, especially in stem leaves. Among in total 22 identified bacterial taxa, the highest level of the taxonomical diversity (H' = 2.01) was revealed in A. halleri basal leaf endophytes originating from Bukowno waste heap area. The 96, 98, 99, and 98% of investigated strains showed tolerant to Cd, Zn, Pb and Cu, respectively. Generally, higher percentages of bacteria could synthesize auxins, siderophores, and acetoin as well as could solubilize phosphate. Nine of waste heap origin bacterial strains were tolerant to toxic metals, showed in vitro PGP traits and are potential candidates for bioremediation.

An Alliance of Trifolium repens-Rhizobium leguminosarum bv. trifolii-Mycorrhizal Fungi From an Old Zn-Pb-Cd Rich Waste Heap as a Promising Tripartite System for Phytostabilization of Metal Polluted Soils.

The Boleslaw waste heap in South Poland, with total soil Zn concentrations higher than 50,000 mg kg-1, 5,000 mg Pb kg-1, and 500 mg Cd kg-1, is a unique habitat for metallicolous plants, such as Trifolium repens L. The purpose of this study was to characterize the association between T. repens and its microbial symbionts, i.e., Rhizobium leguminosarum bv. trifolii and mycorrhizal fungi and to evaluate its applicability for phytostabilization of metal-polluted soils. Rhizobia originating from the nutrient-poor waste heap area showed to be efficient in plant nodulation and nitrogen fixation. They demonstrated not only potential plant growth promotion traits in vitro, but they also improved the growth of T. repens plants to a similar extent as strains from a non-polluted reference area. Our results revealed that the adaptations of T. repens to high Zn-Pb-Cd concentrations are related to the storage of metals predominantly in the roots (excluder strategy) due to nodule apoplast modifications (i.e., thickening and suberization of cell walls, vacuolar storage), and symbiosis with arbuscular mycorrhizal fungi of a substantial genetic diversity. As a result, the rhizobia-mycorrhizal fungi-T. repens association appears to be a promising tool for phytostabilization of Zn-Pb-Cd-polluted soils.

Variability in inorganic As, Sb and Tl species concentrations in waters and bottom sediments of the Klodnica River (Poland).

The study describes the application of new methodologies for the simultaneous determination of As(III)/As(V), Sb(III)/Sb(V) and Tl(I)/Tl(III) ions in waters and bottom sediments of the Klodnica River (Poland) with the hyphenated technique of high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) . Time and spatial correlations were determined in the changes of total and speciation concentrations of the above-mentioned analytes in Klodnica river in 2012. The developed methodologies demonstrate high selectivity and limits of quantification at the level of 0.009-0.120 µg/L. Their repeatability, precision and recovery are appropriate for trace analyses of environmental samples. Time and spatial correlations, and concentrations of inorganic As, Sb and Tl ions demonstrated high variability both in water and bottom sediments.

Impact of the Pb and Zn ore mining industry on the pollution of the Biala Przemsza River, Poland.

The development of mining and metallurgic industries of Pb and Zn ores in the Biala Przemsza catchment area has had a strong influence on the condition of the surface water and bottom sediments. In the following study, total contents of metals and metalloids were researched in the water and bottom sediment samples from the Biala Przemsza River. The samples were collected monthly in 2014 at five sampling points along the river. The research helped to determine correlations between the parameters and components of the water environment (metals/metalloids, cations/anions, pH, Eh, conductivity, carbon (TOC, IC, TC), and suspension). The contents of metals and metalloids were determined with inductively coupled plasma-mass spectrometry (ICP-MS), whereas anions and cations were investigated with ion chromatography (IC). The simplified Community Bureau of Reference (BCR) three-step sequential chemical extraction was performed on Biala Przemsza River bottom sediments collected in April, July, and October. At its lower course, the Biala Przemsza River water did not meet the Polish surface water quality standards. The Biala Przemsza River water is mainly loaded with metals. Toxic concentrations of Cd, Pb, and Zn were observed at sampling points in Okradzionów and Slawków. The toxic Tl concentration was exceeded (2-6 µg/L) at three sampling points. The Biala Przemsza River bottom sediments were composed mostly of medium and fine sand. The BCR extraction of the bottom sediments demonstrated that Cd and Zn were bound to cations/anions and carbonates loosely adsorbed on the bottom sediments in spring and summer. Such a situation was observed at all the sampling points, except for BP3 in Okradzionów. The organic carbon concentration increased along the river course.

Chemometric and environmental assessment of arsenic, antimony, and chromium speciation form occurrence in a water reservoir subjected to thermal anthropopressure.

In the study, arsenic, antimony, and chromium concentrations and selected physicochemical parameters in water and sediment samples from the thermal anthroporessure subjected Rybnik Reservoir (Poland) were determined. As(III), As(V), Sb(III), and Sb(V) ions were successfully separated on Dionex IonPac AS7 column, and Cr(III) and Cr(VI) on Dionex IonPac AG7 column. The obtained limits of detection were 0.18, 0.22, 0.009, 0.012, 0.11, and 0.17 µg/L, respectively. Water and bottom sediment samples were collected monthly at three-point transect between January and November 2013. The As(III) and Sb(III) speciation forms dominated in the bottom water, and Cr(VI) concentration in the bottom water was twice as high as the value measured for the surface water. The oxidized arsenic, antimony, and chromium forms dominated in the bottom sediments in the heated water discharge zone of the Rybnik Power Plant. The location of sampling point had a significant influence on the observed transformations and contents of the analyzed speciation forms. The chemometric analysis coupled with the dissimilarity analysis and principal component analysis helped to visualize the variability in the concentrations of the element speciation forms within the researched period and analyzing correlations.

Development and validation of HPLC-ICP-MS method for the determination inorganic Cr, As and Sb speciation forms and its application for Plawniowice reservoir (Poland) water and bottom sediments variability study.

The optimization of methodology for determination and extraction of inorganic ionic As(III)/As(V), Cr(III)/Cr(VI) and Sb(III)/Sb(V) forms in water and easily-leached fractions of bottom sediments by HPLC-ICP-MS were studied. In paper total concentration of As, Cr, Sb, pH and redox potential were determined. Ions were successfully separated on Dionex IonPac AS7: As(III), As(V), Sb(III), Sb(V) and Dionex IonPac AG7: Cr(III), Cr(VI) with LOD 0.18 µg/L, 0.22 µg/L, 0.009 µg/L, 0.012 µg/L 0.11 µg/L, 0.17 µg/L, respectively. Water and bottom sediments samples were collected monthly from Plawniowice Reservoir, in three-point transects between March and December 2012. In the bottom water predominated As(III) and Cr(III) forms and the highest content of Cr(III) was in the water flowing into the Plawniowice Reservoir. Concentration of Cr(VI) increased in the bottom water in the spring and summer (April-July), while decreasing of the Cr(III) content was associated with the release of Cr(VI) from sediment into the water. Studies have shown that antimony accumulates in reservoir sediments and its reduced form was predominated except May and October-November period when high concentrations of Sb(V) was present. In contrast As(V) was the predominant arsenic form in bottom sediments.

Application of hyphenated techniques in speciation analysis of arsenic, antimony, and thallium.

Due to the fact that metals and metalloids have a strong impact on the environment, the methods of their determination and speciation have received special attention in recent years. Arsenic, antimony, and thallium are important examples of such toxic elements. Their speciation is especially important in the environmental and biomedical fields because of their toxicity, bioavailability, and reactivity. Recently, speciation analytics has been playing a unique role in the studies of biogeochemical cycles of chemical compounds, determination of toxicity and ecotoxicity of selected elements, quality control of food products, control of medicines and pharmaceutical products, technological process control, research on the impact of technological installation on the environment, examination of occupational exposure, and clinical analysis. Conventional methods are usually labor intensive, time consuming, and susceptible to interferences. The hyphenated techniques, in which separation method is coupled with multidimensional detectors, have become useful alternatives. The main advantages of those techniques consist in extremely low detection and quantification limits, insignificant interference, influence as well as high precision and repeatability of the determinations. In view of their importance, the present work overviews and discusses different hyphenated techniques used for arsenic, antimony, and thallium species analysis, in different clinical, environmental and food matrices.

A study on the seasonal mass closure of ambient fine and coarse dusts in Zabrze, Poland.

Diurnal samples of PM(2.5) and PM(2.5-10) were taken in an urban background area in Zabrze (Upper Silesia in southern Poland) in the winter (January-March) and summer (July-September) of 2009. The samples were analyzed for carbon (organic and elemental), water soluble ions (Na(+), NH(4) (+), K(+), Mg(2+), Ca(2+), F(-), Cl(-), NO(3) (-), PO(4) (3-), SO(4) (2-)) and concentrations of 27 elements by using, respectively, a Behr C50 IRF carbon analyzer, a Herisau Metrohm AG ion chromatograph, and a PANalitycal EPSILON 5 X-ray fluorescence spectrometer. To perform the mass closure calculations for both dust fractions in the two periods, the particulate matter (PM) chemical components were categorized into organic matter, elemental carbon, secondary inorganic aerosol, crustal matter, marine components and unidentified matter. The chemical composition of the two dust fractions and the element enrichment coefficients in the two seasons, referred to proper emission profiles, proved about 80% of PM(2.5) and more than 50% (in winter 65%) of PM(2.5-10) mass coming from anthropogenic sources, mainly from fuel combustion and specific municipal emission shaping the winter emission of ambient dust in the area.